Chitosan derived carbon matrix encapsulated CuP2 nanoparticles for

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Chitosan derived carbon matrix encapsulated CuP2 nanoparticles for sodium#ion storage Jian Duan, Shengyuan Deng, Wangyan Wu, Xiang Li, Haoyu Fu, Yunhui Huang, and Wei Luo ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b21213 • Publication Date (Web): 08 Mar 2019 Downloaded from http://pubs.acs.org on March 10, 2019

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ACS Applied Materials & Interfaces

Chitosan derived carbon matrix encapsulated CuP2 nanoparticles for sodium‐ion storage Jian Duan, Shengyuan Deng, Wangyan Wu, Xiang Li, Haoyu Fu, Yunhui Huang, and Wei Luo*

Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai 201804, China *E-mail: [email protected]

KEYWORDS: chitosan, carbon matrix, CuP2 nanoparticles, sodium-ion batteries, monolith

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ABSTRACT: Sodium-ion batteries (SIBs) are more feasible for grid-scale applications than their lithium-ion counterparts when abundant sodium resources with even geographic distribution is taken into consideration. However, developing anode presents a major challenge since standard graphite anode shows a limited Na-ion storage capacity. Here we report a CuCl2/chitosan monolith derived CuP2/C composite where CuP2 nanoparticles are uniformly embedded in carbon matrix. The strong chemical bonding between electron rich groups in chitosan and the heavy metal ion (Cu2+) plays a key role for the synthesis of homogenous monolithic composite and chitosan derived carbon prevents Cu and CuP2 particles from aggregation upon the following thermal reduction and phosphorization. Benefiting from the synergistic effect of small particle size and conductive carbon matrix, CuP2/C composite, as an anode for SIBs, delivers a high reversible capacity of 630 mAh/g at 100 mA/g and a capacity retention ratio of 91% after 200 cycles while bare CuP2 shows a rapid capacity decay within 50 cycles.


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Introduction Lithium-ion batteries (LIBs) have become the default choice for portable electronics since its commercialization in 1991, and are growing in popularity for transportation and grid energy storage applications.1-3 As electric vehicles become popular, the demand for lithium resources increase sharply and questions about alternatives of LIBs are timely. Much greater natural abundance of sodium resources (by a factor of 103) and similar intercalation chemistry to LIBs make sodium-ion batteries (SIBs) a promising substitute.4-7 Unfortunately, commercially available graphite shows a significantly low capacity as SIBs anode. Great efforts for exploiting available anodes have been devoted to amorphous carbon8-12, alloy-based materials1315,

transition metal sulfides16-21 and metal oxides22, 23. As another option, phosphorus

(P) shows the highest theoretical sodium storage capacity and relatively low desodiation potential (~0.6 V).24-26 However, the challenges for its wide application are enormous. P possesses a low electrical conductivity and poses large volume expansion (~ 290 %, by molar volume) upon sodiation.27, 28 The related volume change would cause large anisotropic stresses within the electrode, fracturing and crumbling P particles, which result in a rapid capacity decay. Recently, P-based composites or phosphides have attracted great attention due to their high electric conductivity and much better cycling stability.29-34 Among them, CuP2 gives a high theoretical capacity of 1282 mAh/g based on the conversion and alloy reaction with Na: CuP2 + 6Na ↔ Cu + 2Na3P.35-37 Previous works have demonstrated that designing nanostructured CuP2 and engineering a conductive framework could



promote the electrochemical performance of CuP2. For example, Mathriam’s group chemically bonded CuP2 and C by high energy mechanical milling red P, Cu, and acetylene black carbon. It was demonstrated that the carbon network functioned as a durable matrix in enhancing electrode conductivity and accommodating large volume changes during repeated cycling.38 Most recently, a cross-linking hollow carbon sheet was employed to control particle size of CuP2 and stabilize the porous structure, which can eliminate the negative effects from the large volume change of CuP2.39 Although progress has been made in reducing particle size of CuP2 and adding carbon, it is still a major challenge to develop a scalable approach for practical application. Here we develop a convenient method to fabricate CuP2/C composite with CuP2 nanoparticles embedded in carbon matrix using chitosan, the second most abundant polysaccharide in nature, as Cu2+ absorber and carbon sources. Chitosan has a strong ability to absorb heavy metal ions and is easily to be fabricated in monolithic materials with hierarchical porous structure.40-43 Inspired by this, we obtain a three-dimensional (3D) porous CuCl2/chitosan monolith by freeze drying the CuCl2/chitosan solution, in which Cu2+ ions are adhering on chitosan. As illustrated in Figure 1, a thermal reduction turns CuCl2/chitosan monolith to Cu/C composite and the following phosphorization process gives the final CuP2/C product. More importantly, chitosan derived carbon effectively prevents particle aggregation and maintains the 3D porous structure upon the two-step treatment. The CuP2/C composite delivers a high Na-ion storage capacity of 630 mAh/g at 100 mA/g, excellent rate capability with specific capacity of 413 mAh/g at 400 mA/g and superior cycling stability with capacity retention of 91 % after


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200 cycles. Furthermore, full cells have been assembled by pairing the CuP2/C composite anode and Na3V2(PO4)3 cathode, which show capacity retention of 90% over 100 cycles.

Figure 1. Schematic of the synthesis process of CuP2/C composite. Freeze drying CuCl2/chitosan solution gives CuCl2/chitosan monolith, which is transformed into Cu/C monolith via a thermal reduction. Subsequently, the Cu/C composite is phosphorizated to obtain CuP2/C product where Cu nanoparticles are in-situ transformed to CuP2 nanoparticles embedded in chitosan derived carbon matrix.

EXPERIMENTAL SECTION Materials preparation To prepare CuP2/C composite, CuCl2/chitosan monolith is fabricated via freeze drying the CuCl2/chitosan solution with 0.2 g chitosan and 0.5 g copper chloride dihydrate in 40 ml water. The monolith is thermally treated at 500 oC for 4h in Ar/H2 (5%) to obtain the Cu/C composite. The final CuP2/C product is obtained by heating Cu/C and red P mixture in a sealed stainless-steel vial at 425 oC for 6h. Bare CuP2 is synthesized by heating Cu with red P at 425 oC for 6h. Na3V2(PO4)3 powder is



synthesized via a one-step solid-state method using Na2CO3, V2O5, NH4H2PO4 and glucose as precursors according to our present study. Characterizations and electrochemical measurements The phase information is checked by X-ray diffraction (XRD, PANalytical B.V., Holland). The morphology is observed by scanning electron microscope coupled with energy dispersive X-ray spectroscopy (EDX) detector (FEI, Q250, USA). Transmission electron microscopy (TEM) observation is carried out on a JEOL 2100F microscope. Fourier transform infrared spectroscopy (FTIR) are recorded on a TENSOR Ⅱ (Bruker company, Germany) in the wavenumber range from 400 to 4000 cm-1 at room temperature by averaging 16 scans with a resolution of 4 cm-1 in transmission mode. TG/DTA analysis is performed in air on Pyrisl TGA (PerkinElmer Instruments). N2 sorption measurement is performed on a Quantachrome Autosorb-iQ gas sorptometer. The electrochemical performances are tested with 2032 coin cells. For sodium-ion half cell evaluation, sodium foil is used as both counter and reference electrodes, 1 M solution of NaClO4 in a mixture of ethylene carbonate (EC) and polypropylene carbonate (PC) (1:1 by volume) with 5 vol% addition of fluoroethylene carbonate (FEC) as electrolyte, and Whatman glass fiber as separator. The CuP2/C or bare CuP2 electrode is prepared by casting the slurry of 80 wt% active material, 10 wt% super P and 10 wt% polyvinylidene fluoride (PVDF) onto a copper foil, and then dried in a vacuum oven at 80 °C for 24 h. The active mass loading in the electrode is around 2 mg/cm2. For full cells, CuP2/C electrode was used as anode and NVP electrode as cathode. NVP electrode is prepared by casting the slurry of 80 wt% active material, 10 wt% super P


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and 10 wt% polyvinylidene fluoride (PVDF) onto an aluminum foil, followed with 80 oC

drying. The electrolyte and separator used are the aforementioned ones of sodium-

ion half cell. The galvanostatic charge/discharge tests are carried out using a battery tester (Neware, China) at 25 oC. Cyclic voltammetry (CV) is measured on an electrochemical workstation (Biologic VMP3). Results and Discussion Figure 2a shows a digital image of the 3D porous CuCl2/chitosan monolith after freeze drying, where the sublimation of solvent left a large number of pores in the monolith. By a following thermal treatment in Ar/H2 (5%), the monolith structure maintains well while the color changing from yellow (CuCl2) to pinkish-orange (metallic Cu), as shown in Figure 2b. XRD pattern of the Cu/C monolith indicates that CuCl2 is thermally reduced to metallic Cu while chitosan acts as a carbon sources to enable a Cu/C composite (Figure S1). The content of carbon in the composite is calculated to be 30.4%, as characterized by TG/DTA method (see more details in Figure S2). Interestingly, the following phosphorization process don’t affect the overall monolith morphology neither (Figure 2c). XRD results confirm the effective phosphorization that Cu is converted to be CuP2 with a monoclinic phase (Figure 2d). A SEM image of the CuCl2/chitosan monolith exhibits a porous structure consisted of CuCl2/chitosan sheets (Figure 2e). After the following thermal reduction process, Cu/C composite maintains a porous monolithic structure and Cu/C sheets with several microns thick interconnect with each other. Surprisingly, there are no metallic Cu particles aggregation on the surface (Figure 2f, g). The corresponding EDX images in



Figure 2h, i show a well distributed Cu on the whole carbon sheet, indicating chitosan derived carbon plays a key role in preventing Cu particles from aggregation. Elemental nitrogen (N) is also detected since chitosan is a linear polysaccharide, which composes of a substantial number of acetylated units (Figure S3). According to previous reports, N-doped carbon derived from chitosan has a high conductivity, indicating a great promise for battery applications.44 The phosphorization process is conducted just above the sublimation temperature of red phosphorus to realize the successful transformation of Cu nanoparticles to CuP2 nanoparticles, which disperse uniformly on the carbon sheets without particle aggregation (Figure 2j-m). N2 sorption-desorption isotherm of CuP2 was shown in Figure S4 with the calculated BET surface area at 188.1 m2/g.

Figure 2. Digital images of (a) the CuCl2/chitosan, (b) Cu/C and (c) CuP2/C monoliths. The 3D porous structure maintains well upon the thermal reduction and phosphorization. (d) XRD pattern of CuP2/C monolith (inset is structure of CuP2). (e) A SEM image of CuCl2/chitosan monolith after freeze drying. SEM and corresponding EDX images of (f-i) Cu/C and (j-m) CuP2/C monoliths.


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TEM observation is used to capture fine details of the Cu/C and CuP2/C monoliths. As shown in Figure 3a, Cu nanoparticles are uniformly embedded in carbon nanosheets of the Cu/C composite. The particle size of Cu is around 4 nm without aggregation due to the restriction of chitosan derived carbon matrix. Lattice fringes with d-spacing of 0.209 nm can be detected, which corresponds to the (1 1 1) planes of Cu (Figure 3b). After the phosphorization process, Cu nanoparticles transform into CuP2 nanoparticles embedded in carbon matrix (Figure 3c). High-resolution TEM image in Figure 3d further presents lattice fringes of CuP2 with d-spacing of 0.289 nm, corresponding to the (-1 1 2) plane of CuP2. Here, we succeed in fabricating CuP2/C composite, of which CuP2 nanoparticles are homogenously embedded in carbon matrix.

Figure 3. Low-magnification TEM and HRTEM images of (a, b) Cu/C composite and (c, d) CuP2/C composite. Cu nanoparticles with an average particle size of 4 nm are phosphorizated into CuP2 nanoparticles where chitosan-derived carbon matrix play a critical role in limiting the particle aggregation upon thermal reduction and phosphorization.



The formation mechanism of the CuP2/C composite is further investigated. Typically, chitosan, produced commercially by deacetylation of chitin, consists of protophilic organic groups, such as C=O, N–H, C–O and C–N etc., which offer chitosan the strong ability to absorb metal ions (Figure S5). FTIR spectrum of chitosan in Figure 4 exhibits two obvious absorb peaks at 1628.15 and 1518.49 cm-1, corresponding to C=O stretch of amide bond and N–H bending vibration of secondary amide, respectively.45 The corresponding peaks in FTIR spectrum of CuCl2/chitosan monolith shift to lower wavenumbers (1589.54 and 1516.74 cm-1), which is attributed to the electrostatic interactions between Cu2+ and protophilic organic groups of chitosan.46 The peaks of chitosan located at 1382.69 and 1089.36 cm-1, due to the C-N and C-O, also shift to lower wavenumbers after the adsorption of CuCl2. The FTIR results reveal that –OH, C=O, N–H, C–N and C–O groups in chitosan are the active sites for Cu2+ absorption. The strong interaction between Cu2+ and chitosan ensures homogenous mixing and prevents CuCl2 from becoming large particles during the freeze drying process. During the following thermal treatment and phosphorization, Cu2+ ions are insitu reduced to Cu nanoparticles and converted to CuP2 nanoparticles while chitosan becomes carbon and restrict the growth of Cu and CuP2 nanoparticles.


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Figure 4. FTIR spectra of chitosan (black line) and CuCl2/chitosan monolith (blue line). Compared to bare chitosan, electrostatic interactions between the heavy metal ions (Cu2+) and electron rich groups in chitosan causes the change in the bond length, leading to peak shift.

The electrochemical performance of CuP2/C composite is evaluated in 2032-type half cells. Figure 5a shows the CV curves for the initial three cycles at a scan rate of 0.1 mV/s. There are two broad reduction waves around 0.35 and 0.01 V of the cathodic sweep, which are ascribed to the multistep sodiation of CuP2 to Cu and Na3P. In the ensuing anodic sweep, two broad waves appear at 0.65 and 0.88 V, showing a reversible desodiation process.37, 38 It is noticed that current in the first CV cycle is smaller than the following cycles, suggestive of an activation process since CuP2 nanoparticles are well embedded in carbon matrix. After the first cycle, CV curves overlap and remain steady, showing a great stability. As shown in Figure 5b, the CuP2/C composite electrode exhibits an excellent rate capability with capacities of 630, 519, 413 and 263 mAh/g at the current densities of



100, 200, 400 and 800 mA/g, respectively. The specific capacity and current densities are calculated based on the total mass of CuP2/C composite. When the current density is rested to 100 mA/g, the capacity recovers to 626 mAh/g. The excellent rate capability is due to the well combination of CuP2 nanoparticles and carbon matrix. The CuP2/C composite also shows a stable cycle performance (Figure 5c). At the beginning, the capacity increases slightly in few cycles, which is due to the activation process, agreeing well with the CV results. After 200 cycles, the capacity maintains a specific capacity of 477 mAh/g, giving a capacity retention of 91%. We also prepare bare CuP2 by phosphorization of Cu mesh as a control. The bare CuP2 electrode delivers a slightly higher capacity at the beginning. However, the capacity fades rapidly from 625 to 95 mAh/g within 50 cycles. As known, the large volume change of CuP2 upon electrochemical cycling results in electrode pulverization and electrical contact loss, leading to the fast capacity decay. On the other side, carbon matrix in CuP2/C composite acts as a buffer to accommodate the volume change and enables the electronic pathway at the same time. In addition, the CuP2/C composite shows high specific lithium-ion storage capacity (see more details in Figure S6). We further paired CuP2/C composite with NASICON-type Na3V2(PO4)3 (NVP) cathode to investigate the applicability of CuP2/C in full cells. NVP is prepared according to our previous study (Figure S7-9).47 According to the average working potentials of 3.4 and 0.8 V vs. Na+/Na for the NVP cathode and the CuP2/C anode (Figure 5d), the full cell operates at around 2.6 V, as shown in Figure 5e. The full cell shows an excellent cycle stability with a 90.6% capacity retention and nearly 100%


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Coulombic efficiency over 100 cycles (Figure 5f). The excellent cycling stability is ascribed to superior cycle stability of both NVP cathode and CuP2/C composite anode.

Figure 5. (a) CV curves for the first three cycles of CuP2/C electrode in half cell. (b) Rate capability and Coulombic efficiency of CuP2/C electrode in half cell at different current rates. (c) Cycling performance of CuP2/C and bare CuP2 electrodes at 200 mA/g. (d) Typical charge/discharge voltage profiles of the CuP2/C and NVP electrodes in half cells at 0.2 C. (e) Voltage profile of the full cell (NVP | CuP2/C) at 0.2C (1C = 100 mA/g). (f) Cycling performance and Coulombic efficiency of the full cell at 0.4C.

CONCLUSIONS In summary, we have taken advantages of chitosan’s high adsorption activity and facile fabrication of monolithic materials to synthesize CuP2/C composite via freeze drying, thermal reduction and phosphorization. CuP2 nanoparticles are uniformly embedded in chitosan derived carbon matrix, which exhibit a high reversible capacity, superior rate capacity and stable cycling performance, with 91% capacity retention after



200 cycles. A full cell of NVP and CuP2/C also exhibits stable cycling performance. We demonstrate that chitosan’s absorption capability for Cu2+ enables the homogenous CuCl2/chitosan monolith and chitosan derived carbon matrix acts as an agent for limiting the growth and aggregation of Cu and CuP2 nanoparticles during thermal treatment. Moreover, the carbon matrix can accommodate the volume change and maintain an electron pathway for CuP2 nanoparticles upon the electrochemical charge/discharge process. We believe that our methodology is potentially competitive for a practical production of nanosized metal phosphides and could be extensively applied to other metal-based electrode materials for battery applications.

ASSOCIATED CONTENT Supporting Information. XRD pattern of the Cu/C monolith; TG/DTA curves of the Cu/C composite and XRD pattern of Cu/C composite after TG/DTA test; SEM and corresponding EDX images of the Cu/C composite; a schematic graph of the interaction between the chitosan and Cu2+; charge/discharge profiles of NVP electrode in NVP|Na half cell at different current rates at voltage ranging from 2.2-4.0 V. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]


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Notes The authors declare no competing financial interest. ACKNOWLEDGEMENTS

We are grateful for the financial support by National Natural Science Foundation of China (No. 51802224 and 51632001). REFERENCES 1.

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Chitosan derived carbon matrix encapsulated CuP2 nanoparticles for

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